Synthetic resin composition and methods of utilizing the same

ABSTRACT

Methods of applying stable synthetic resin compositions to porous material the synthetic resin compositions comprising: (1) a synthetic resin; (2) a polyvalent metal complex coordination compound; and (3) a water-soluble, ionically active ammonium or alkali metal salt of an acid capable of being chemically converted into an ionically inactive polyvalent metal salt of said acid by chemical reaction and precipitation or sequestration of said polyvalent metal salt, and substantially immediately destroying the stability of the synthetic resin compositions to precipitate the resin on the porous materials under controlled migration conditions.

nited States Patent Drelich et al.

[451 Nov. 19, 1974 SYNTHETIC RESIN COMPOSITION AND METHODS OF UTILIZINGTHE SAME [75] Inventors: Arthur H. Drelich, Plainfield;

George J. Lukacs, Perth Amboy, both of NJ.

[73] Assignee: Johnson & Johnson, New

Brunswick, NJ.

[22] Filed: June 7, 1972 [21] Appl. No.2 260,613

[52] U.S. Cl ll7/62.l, 117/38, 117/47 A, 117/47 R, l17/62.2, 117/140 A,260/29.6

MM, 260/29.6 MP, 260/29.6 MN, 260/29.7

M, 260/29.7 P, 260/29.7 N

[51] Int. Cl B44d 1/44, B44d 1/02 [58] Field of Search..... 260/29.7 N,29.7 P, D10. 4; 117/38, 47 R, 47 A, 62.1, 62.2, 140 A, 105.5

[56] References Cited UNITED STATES PATENTS 3,536,518 10/1970 Drelichll7/62.1 X 3,539,434 11/l970 Spaulding 117/140 A 3,578,485 5/1971 lmotoet al. ll7/62.2 3,594,210 7/1971 Drelich 117/38 3,647,507 3/1972Ashcraft 117/38 3,649,330 3/1972 Drelich ll7/38 3,650,805 3/1972 lmotoet al. 1 17/622 3,674,726 7/1972 Kirk 260/29.7 P 3,706,595 12/1972Drelich et a1... 117/38 3,720,562 3/1973 Drelich 156/291 PrimaryExaminerWilliam D. Martin Assistant Examiner-William H. Schmidt [5 7]ABSTRACT Methods of applying stable synthetic resin compositions toporons material the synthetic resin compositions comprising: (1) asynthetic resin; (2) a polyvalent metal complex coordination compound;and (3) a water-soluble, ionically active ammonium or alkali metal saltof an acid capable of being chemically converted into an ionicallyinactive polyvalent metal salt of said acid by chemical reaction andprecipitation or sequestration of said polyvalent metal salt, andsubstantially immediately destroying the stability of the syntheticresin compositions to precipitate the resin on the porous materialsunder controlled migration conditions.

16 Claims, 1 Drawing Figure SYNTHETIC RESIN COMPOSITION AND METHODS OFUTILIZING THE SAME GENERAL BACKGROUND OF THE INVENTION The presentinvention relates to synthetic resin compositions and to methods ofutilizing the same. More particularly, the present invention relates tosynthetic resin compositions and to methods of applying such syntheticresin compositions to porous or absorbent materials and controllingtheir spreading, diffusing, or migrating thereon or their penetratingtherein. Even more particularly, the present invention is concerned withthe so-called bonded, nonwoven textile fabrics, i.e., fabrics producedfrom textile fibers without the use of conventional spinning, weaving,knitting or felting operations. Although not limited thereto, theinvention is of primary importance in connection with nonwoven fabricsderived from oriented or carded fibrous webs composed of textile-lengthfibers, the major proportion of which are oriented predominantly in onedirection.

Typical of such fabrics are the so-called MAS- SLINN nonwoven fabrics,some of which are described in greater particularity in US. Pat. Nos.2,705,687and 2,705,688, issued Apr. 5, 1955, to D. R. Petterson et al.and I. S. Ness et al., respectively.

Another aspect of the present invention is its application to nonwovenfabrics wherein the textile-length fibers were originally predominantlyoriented in one direction but have been reorganized and rearranged inpredetermined designs and patterns of fabric openings and fiber bundles.Typical of such latter fabrics are the so-called KEYBAK bundled nonwovenfabrics, some of which are described in particularity in US. Pat. Nos.2,862,25l and 3,033,721, issued Dec. 2, 1958 and May 8, 1962,respectively, to F. Kalwaites.

Still another aspect of the present invention is its application tononwoven fabrics wherein the textilelength fibers are disposed at randomby air-laying techniques and are not predominantly oriented in any onedirection. Typical nonwoven fabrics made by such procedures are termedisotropic nonwoven fabrics and are described, for example, in US. Pat.Nos. 2,676,363 and 2,676,364, issued Apr. 27, 1954 to C. H. Plummer etal.

And still another aspect of the present invention is its application tononwoven fabrics which comprise textile-length fibers and which are madebasically by conventional or modified aqueous papermaking techniquessuch as are described in greater particularity in pending patentapplication Ser. No. 4,405, filed Jan. 20, 1970 by P. R. Glor and A. H.Drelich. Such fabrics are also basically isotropic and generally havelike properties in all directions.

The conventional base starting material for the majority of thesenonwoven fabrics is usually a fibrous web comprising any of the commontextile-length fibers, or mixtures thereof, the fibers varying inaverage length from approximately inch to about 2% inches. Exemplary ofsuch fibers are the natural fibers such as cotton and wool and thesynthetic or man-made cellulosic fibers, notably rayon or regeneratedcellulose.

Other textile length fibers of a synthetic or man-made origin may beused in various proportions to replace either partially or perhaps evenentirely the previously named fibers. Such other fibers include:polyamide fibers such as nylon 6, nylon 66, nylon 610, etc.; polyesterfibers such as Dacron, Fortrel and Kodeh acrylic fibers such asAcrilan," Orlon and Creslan; modacrylic fibers such as Verel and Dynel;"polyolefinic fibers derived from polyethylene and polypropylene;cellulose ester fibers such as Amel and Acele; polyvinyl alcohol fibers;etc.

These textile length fibers may be replaced either partially or entirelyby fibers having an average length of less than about 7% inch and downto about inch. These fibers, or mixtures thereof, are customarilyprocessed through any suitable textile machinery (e.g., a

conventional cotton card, a Rando-Webber," a papermaking machine, orother fibrous web producing apparatus) to form a web or sheet of looselyassociated fibers, weighing from about grains to about 2,000 grains persquare yard or even higher. 3

If desired, even shorter fibers, such as wood pulp fibers or cottonlinters, may be used in varying proportions, even up to 100 percent,where such shorter length fibers can be handled and processed byavailable apparatus. Such shorter fibers have lengths less than A inch.

The resulting fibrous web or sheet, regardless of its method ofproduction, is then subjected to at least one of several types ofbonding operations to anchor the individual fibers together to form aself-sustaining web. One method is to impregnate the fibrous web overits entire surface area with various well-known bonding agents, such asnatural or synthetic resins. Such over-all impregnation produces anonwoven fabric of good longitudinal and cross strength, acceptabledurability and washability, and satisfactory abrasion resistance.However, the nonwoven fabric tends to be somewhat stiff and boardlike,possessing more of the properties and characteristics of paper or boardthan those of a woven or knitted textile fabric. Consequently, althoughsuch over-all impregnated nonwoven fabrics are satisfactory for manyuses, they are still basically unsatisfactory as general purpose textilefabrics.

Another well-known bonding method is to print the fibrous webs withintermittent or continuous straight or wavy lines, or areas of binderextending generally transversely or diagonally across the web andadditionally, if desired, along the fibrous web. The resulting nonwovenfabric, as exemplified by a product disclosed in the Goldman US. Pat.No. 2,039,312 and sold under the trademark, MASSLINN, is far moresatisfactory as a textile fabric than over-all impregnated webs in thatthe softness, drape and hand of the resulting nonwoven fabric morenearly approach those of a woven or knitted textile fabric.

The printing of the resin binder on these nonwoven webs is usually inthe form of relatively narrow lines, or elongated rectangular,triangular or square areas, or annular, circular, or elliptical binderareas which are spaced apart a predetermined distance which, at itsmaximum, is preferably slightly less than the average fiber length ofthe fibers constituting the web. This is based on the theory that theindividual fibers of the fibrous web should be bound together in as fewplaces as possible.

The nominal surface coverage of such binder lines or areas will varywidely depending upon the precise properties and characteristics ofsoftness, drape, hand and strength which are desired in the final bondedproduct. In practice, the nominal surface coverage can be designed sothat it falls within the range of from about percent to about 50 percentof the total surface of the final product. Within the more commericalaspects of the present invention, however, nominal surface coverages offrom about 12 percent to about 40 percent are preferable.

Such bonding increases the strength of the nonwoven fabric and retainssubstantially complete freedom of movement for the individual fiberswhereby the desirable softness, drape and hand are obtained. Thisspacing of the binder lines and areas has been accepted by the industryand it has been deemed necessarily so, if the stiff and board-likeappearance, drape and hand of the over-all impregnated nonwoven fabricsare to be avoided.

The nonwoven fabrics bonded with such line and area binder patterns havehad the desired softness, drape and hand and have not been undesirablystiff or board-like. However, such nonwoven fabrics have also possessedsome disadvantages.

For example, the relatively narrow binder lines and relatively smallbinder areas of the applicator (usually an engraved print roll) whichare laid down on the fibrous web possess specified physical dimensionsand inter-spatial relationships as they are initially laid down.Unfortunately, after the binder is laid down on the wet fibrous web andbefore it hardens or becomes fixed in position, it tends to spread,diffuse or migrate whereby its physical dimensions are increased and itsinter-spatial relationships decreased. And, at the same time, the binderconcentration in the binder area is lowered and rendered less uniform bythe migration of the binder into adjacent fibrous areas. One of theresults of such migration is to make the surface coverage of the binderareas increase whereby the effect of the intermittent bonding approachesthe effect of the overall bonding. As a result, some of the desiredsoftness, drape and hand are lost and some of the undesired propertiesof harshness, stiffness and boardiness are increased.

Various methods have been proposed to prevent or to at least limit suchspreading, diffusing or migration tendencies of such intermittent bindertechniques.

For example, US. Pat. No. 3,009,822, issued Nov. 21, 1961 to A. H.Drelich et al., discloses the use of a nonmigratory regeneratedcellulose viscose binder which is applied in intermittent fashion tofibrous webs under conditions wherein migration is low and theconcentration of the binder in the binder area is as high as 35 percentby weight, based on the weight of the fibers in these binder areas. Suchviscose binder possesses inherently reduced spreading, diffusing andmigrating tendencies, thereby increasing the desired softness, drape andhand of the resulting nonwoven fabric. This viscose binder has foundacceptance in the industry but the use of other more versatile bindershas always been sought.

Resins, or polymers as they are often referred to herein asinterchangeable terms, are high molecular weight organic compounds and,as used herein, are of a synthetic or man-made origin. These syntheticor man-made polymers have a chemical structure which usually can berepresented by a regularly repeating small unit, referred as a mer, andare formed usually either by an addition or a condensationpolymerization of one or more monomers. Examples of addition polymersare the polyvinyl chlorides, the polyvinyl acetates,

the polyacrylic resins, the polyolefms, the synthetic rubbers, etc.Examples of condensation polymers are the polyurethanes, the polyamides,the polyesters, etc.

Of all the various techniques employed in carrying out polymerizationreactions, emulsion polymerization is one of the most commonly used.Emulsion polymerized resins, notably polyvinyl chlorides, polyvinylacetates, carboxylated styrene butadiene rubbers, and polyacrylicresins, are widely used throughout many industries. Such resins aregenerally produced by emulsifying the monomers, stabilizing the monomeremulsion by the use of various surfactant systems, and then polymerizingthe monomers in the emulsified state to form a stabilized resin polymer.The resin polymer is usually dispersed in an aqueous medium as discreteparticles of colloidal dimensions (1 to 2 microns diameter or smaller)and is generally termed throughout the industry as a resin dispersion,"or a resin emulsion or latex.

Generally, however, the average particle size in the resin dispersion isin the range of about 0.1 micron (or micrometer) diameter, withindividual particles ranging up to l or 2 microns in diameter andoccasionally up to as high as about 3 or 5 microns in size. The particlesizes of such colloidal resin dispersions vary a great deal, not onlyfrom one resin dispersion to another but even within one resindispersion itself.

The amount of resin binder solids in the resin colloidal aqueousdispersion varies from about 1/10 percent solids by weight up to aboutpercent by weight or even higher solids, generally dependent upon thenature of the monomers used, the nature of the resulting polymer resin,the surfactant system employed, and the conditions under which thepolymerization was carried out.

These resin colloidal dispersions, or resin emulsions, or latexes, maybe anionic, non-ionic, or even polyionic and stable dispersions areavailable commercially at pl-ls of from about 2 to about 1 1.

As will be pointed out in greater detail, such resin dispersions areused in the present inventive concept at alkaline pH ranges. Variousalkaline reagents, such as ammonia, are therefore added to bring the pHout of the acid range.

The amount of resin which is applied to the porous or absorbent materialvaries within relatively wide limits, depending upon the resin itself,the nature and character of the porous or absorbent materials to whichthe resins are being applied, its intended use, etc. A general range offrom about 4 percent by weight up to about 50 percent by weight, basedon the weight of the porous or absorbent material, is satisfactory undersubstantially all uses. Within the more commercial limits, however, arange of from about 10 percent to about 30 percent by weight, based onthe weight of the porous or absorbent material, is preferred.

Such resins have also found use in the coating industries for thecoating of knitted fabrics, woven fabrics, paper, paper products,leather, and other materials. The resins are also used as adhesives forlaminating films, sheets and like materials or for bonding fibrous webs.These resins have also found wide use as additives in the manufacture ofpaper, the printing industry, the painting industry, the decorativeprinting of textiles, and in other industries.

In most instances, the resin is colloidally dispersed in water and, whenapplied from the aqueous medium to a porous or absorbent sheet materialwhich contains additional water is carried by the water until the wateris evaporated or otherwise driven off. If it is desired to place theresin only on the surface of the wet porous or absorbent sheet materialand not to have the resin penetrate into the porous or absorbent sheetmaterial, such is usually not possible inasmuch as diffusion takes placebetween the aqueous colloidal resin and the water in the porousmaterial. In this way, the colloidal resin tends to spread into andthroughout the porous material and does not remain merely on itssurface.

Or, if it is desired to deposit the resin in a specific intermittentprint pattern, such as is used in bonding nonwoven fabrics, the aqueouscolloid tends to diffuse, spread or migrate and to wick along theindividual fibers and to carry the resin with it beyond the confines ofthe nominal intermittent print pattern. As a result, although initiallyplaced on the nonwoven fabric in a specific intermittent print pattern,the ultimate pattern goes far beyond that due to the spreading ofmigration which takes place due to the diffusion of the water and theresin, until the water is evaporated or otherwise driven off.

We have discovered new resin binder compositions containing polymerscolloidally dispersed in aqueous media and new methods of applying suchresin binder compositions to porous or absorbent materials, asenumerated herein, whereby the resins are applied in a controlled,relatively nonmigrating manner. If it is desired that the resin beplaced only on the surface of the porous or absorbent material, ourcompositions and methods will allow this to be done. Furthermore, if itis desired that the resin be impregnated throughout the material, fromone surface to the other surface, again, our compositions and methodswill allow this to be done.

SPECIFIC BACKGROUND OF THE INVENTION In copending, commonly-assignedpatent applications Ser. No. 65,880 filed Aug. 21, 1970, now U.S. Pat.No. 3,720,562 which issued Mar. 13, 1973, and Ser. No. 66,003 filed Aug.21, 1970, now abondoned, and Ser. No. 109,026 filed Jan. 22, 1971, nowU.S. Pat. No. 3,706,595 which issued Dec. 19, 1972, there are disclosedvarious synthetic resin compositions and methods of utilizing the sameby application to porous or absorbent materials. Basically, thesemethods disclose applying stable synthetic resin compositions underalkaline conditions to porous or absorbent materials which werepreviously treated and wetted with controlled concentrations or amountsof acidic media, aqueous media, or simply water. When the syntheticresin compositions were applied to the pretreated porous or absorbentmaterials, their stability was altered and destroyed by the resultingaltered acidic or dilutive conditions and they immediately coagulatedand precipitated on the porous or absorbent materials under controlledmigration conditions.

More specifically, U.S. Pat. No. 3,706,595 discloses methods of applyingstable synthetic resin compositions as described herein and having analkaline pH to porous materials and controlling the migration of suchstable synthetic resin compositions on such porous materials bydestroying the stability of such synthetic resin compositions bydiluting the same substantially immediately after being applied to suchporous materials.

And, also more specifically, U.S. Pat. No. 3,720,562 discloses methodsof applying stable synthetic resin compositions as described herein andhaving an alkaline pH to porous materials and controlling the migrationof such stable synthetic resin compositions on such porous materials bydestroying the stability of such synthetic resin compositions byacidifying the same-substantially immediately after being applied tosuch porous materials.

THE METHODS Normally, the methods disclosed in these patent applicationsand in the present case involve the use of standard or conventionalapparatus, such as described in FIG. 9 of U.S. Pat. No. 3,009,822. Suchmethods employ an adjustable upper rotatable back-up roll and anadjustable lower rotatable engraved print roll or applicator roll, withthe porous or absorbent materials passing under adjustable pressurethrough the nip there between. In contact with the applicator roll was alowermost rotatable pick-up roll partially immersed in a bath of thesynthetic'resin composition, which pick-up roll picked up the syntheticresin composition and transferred it to the applicator roll whichapplied it to the porous or absorbent materials.

THE APPARATUS A typical arrangement of such apparatus is shown in theFIGURE for illustrative but not for limitative purposes. In this FIGURE,there is shown an adjustable upper rotatable back-up roll 10, rotatingon a rotatable shaft 12, in adjustably controlled pressure contact witha lower rotatable engraved print roll or applicator roll 14 rotating ona rotatable shaft 16. In contact with the applicator roll 14 is alowermost rotatable pick-up roll 18 rotating on a rotatable shaft 20 andbeing partially immersed in a bath 22 of the synthetic resincomposition, which pick-up roll 18 picks up the synthetic resincomposition 24 and transfers it to the applicator roll 14 which appliesit to a porous or absorbent material W passing through the adjustablepressure nip of back-up roll 10 and applicator roll 14. All these rollsare adjustable whereby the pressure applied to the porous or absorbentmaterial W is adjusted to control the amount of pick-up of the syntheticresin composition 24 on the porous or absorbent material W. A doctorblade 26 is employed to prevent build-up of the resin latex on thepick-up roll 18. This apparatus is generally conventional and standardand other equivalent forms of apparatus are of use.

PRIOR OPERATING DIFFICULTIES On occasion, it has been noted that thesynthetic resin composition lost its stability and thickened orprematurely coagulatedand precipitated in the bath 22 itself, prior toapplication to the porous or absorbent material W. As a result,operating difficulties were consequently occasionally encountered.

The premature coagulation and precipitation was evidenced primarily by athickening or setting-up of the synthetic resin composition in the bath,particularly during the running of the operation.

Also, in some cases, it has been noted that a synthetic resincomposition having a viscosity, for example, a 1,000 centipoises, whenoriginally prepared, thickened to a viscosity of 20,000 centipoises orhigher in a period of 1 week storage, prior to plant operation. Acomparable synthetic resin composition, when protected by theapplication of the present invention, thickened only slightly to aviscosity of 1,040 centipoises.

It is a primary purpose of the present inventive concept to prevent suchundesirable unstability, thickening and setting-up and prematurecoagulation and precipitation of the synthetic resin compositions duringstorage and during actual manufacturing operations. It

' is a further purpose of our invention to permit the formulation ofmore effective and versatile resin compositions.

GENERAL STATEMENT OF THE INVENTION It has been discovered that suchprimary purpose and other advantages and benefits to be describedhereinafter are realized by adding to the synthetic resin compositionsdescribed in said patent applications controlled amounts of astabilizing and anti-coagulating and precipitating agent comprising awater-soluble, ionically active ammonium or alkali metal salt of an acidcapable of being chemically converted into an ionically inactivepolyvalent metal salt of said acid by chemical reaction andprecipitation or sequestration of said polyvalent metal salt.

It has not been established beyond any doubt but it is believed thatrelatively small amounts of polyvalent metal cations spontaneouslyionize away from the polyvalent metal complex coordination compoundafter formulation and during storage before use and that theserelatively small amounts of polyvalent metal cations trigger thepremature thickening, setting-up, coagulation or precipitation in thebath prior to application to the porous or absorbent materials.

It is also believed that such undesirable premature coagulation andprecipitation by the relatively small amounts of polyvalent metalcations is promoted and accelerated by unspecified amounts of acidicmedia, aqueous media, or simply water, which are pressed out of theporous materials as they pass through the nip of the back-up roll andapplicator roll to drain downwardly into the synthetic resin compositionin the bath. This, of course, changes the pH and/or concentration of thecomplex coordination compound whereby its stability is changed.

The addition of the stabilizing and anti-coagulating andanti-precipating agent serves to render the liberated polyvalent metalcations innocuous and ionically inactive by chemical reaction andprecipitation or sequestration of the polyvalent metal cations. Theaction of the stabilizing and anti-coagulating agent is thus actually ascavenging action. In this way, the synthetic resin is unaffected andthe viscosity of the synthetic resin composition is relativelystabilized.

in order to understand and explain the probable mechanism of the actionstaking place, it is instructive to show a typical equilibrium reactioninvolving a divalent complex metal compound:

Prior to this invention, problems were sometimes encountered by thepremature liberation of the M cation which caused premature thickeningor coagulation of the resin component in the binder formulation. Thisliberation of the metal cation can be triggered by an increase inconcentration of H 0 by dilution or a decrease in concentration ofNH.,OH by dilution. neutralization, or evaporation. The scavengingagents which we have discovered effectively inactivate the liberated Mcation.

Based on simple considerations of reaction kinetics, the removal of Mfrom the system should shift the equilibrium to continuously form moreionic M cations to maintain the constancy of the value of the reactionconstant k. Unexpectedly and surprisingly. this does not appear tohappen, or to happen so slowly that we can increase the stability of aformulation from several hours to many weeks.

THE S Y N lHETIC RESIN The improved synthetic resin compositions of thepresent invention comprise from about 0.1 percent to about 60 percent byweight on a solids basis of a colloidal synthetic resin and may be of aself cross-linking type, or an externally cross-linking type, or may notbe cross-linked.

Specific examples of such colloidal synthetic resins -include: polymersand copolymers of vinyl halides such as plasticized and unplasticizedpolyvinyl chloride, polyvinyl chloride-polyvinyl acetate, ehtylene-vinylchloride, etc.; polymers and copolymers of vinyl esters such asplasticized and unplasticized polyvinyl acetate, ethylene-vinyl acetate,acrylic-vinyl acetate, etc.; polymers and copolymers of the polyacrylicresins such as ethyl acrylate, methyl acrylate, butyl acrylate,ethyl-butyl acrylate, ethyl hexyl acrylate, hydroxyethyl acrylate,dimethyl amino ethyl acrylate, etc.; polymers and copolymers of thepolymethacrylic resins such as methyl methacrylate, ethyl methacrylate,isopropyl methacrylate, butyl methacrylate, etc.; polymers andcopolymers of acrylonitrile, methacrylonitrile, acrylamide, N- isopropylacrylarnide, N-rnethylol acrylamide, methacrylamide, etc.; vinylidenepolymers and copolymers, such as polyvinylidene chloride, polyvinylidenechloride-vinyl chloride, polyvinylidene chloride-ethyl acrylate,polyvinylidene chloride-vinyl chlorideacrylonitrile, etc.; polymers andcopolymers of polyolefinic resins including polyethylene, polypropylene,ethylene-vinyl chloride and ethylene-vinyl acetate which have beenlisted previously; the synthetic rubbers such as 1,2-butadiene,1,3-butadiene, 2-ethyl-l,3- butadiene, high, medium and carboxylatedbutadieneacrylonitrile, butadiene-styrene, chlorinated rubber, etc.,natural latex; the polyurethanes; the polyamides; the polyesters; thepolymers and copolymers of the styrenes including styrene, 2-methylstyrene, 3-methyl styrene, 4-methyl styrene, 4-ethyl styrene, 4-butylstyrene; natural latex; phenolic emulsions; etc.

These resins may be used either as homopolymers comprising a singlerepeating monomer unit, or they may be used as copolymers comprisingtwo, three, or more different monomer units which are arranged in randomfashion, or in a definite ordered alternating fashion, withinthe polymerchain. Also included within the inventive concept are the block polymerscomprising relatively long blocks of different monomer units in apolymer chain and graft polymers comprising chains of one monomerattached to the backbone of another polymer chain.

Other synthetic resins of particular applicability within the principlesof the present inventive concept are colloidal synthetic resinscontaining a coordinating ligand.

The coordinating ligand is normally an acidic or proton donor group,especially those containing terminal hydroxy groups. Examples ofhydroxy-containing coordinating ligands are: hydroxy -OH; carboxy-COOl-l; sulfino -SO(Ol-l) sulfo -SO (Ol-l); sulfonoamino -NHSO (OH);aci-nitro=NO(Ol-l); -NHOH; hydroxyimino=NOI-l; etc. It is to be observedthat these hydroxy-containing radicals contain a hydrogen atom which iscapable of dissociating to form an H ion or proton.

The colloidal synthetic resins possessing a hydroxycontainingcoordinating ligand are obtained by copolymerizing: 1 from about 92percent by weight to about 99 percent by weight of a monomer or amixture of monomers of the group comprising vinyl halide, vinyl ester,or vinyl ether monomers including, for example, vinyl chloride, vinylacetate and vinyl ethyl ether; olefin monomers such as ethylene andpropylene; acrylic and methacrylic monomers including, for example,ethyl acrylate, ethyl hexyl acrylate, methyl acrylate, propyl acrylate,butyl acrylate, hydroxyethyl acrylate, dimethyl amino ethyl acrylate,methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butylmethacrylate, acrylonitrile, methacrylonitrile, acrylamide, N-isopropylacrylamide, N-methylol acrylamide, methacrylamide; vinylidene monomerssuch as vinylidene chloride; diene monomers including, for example1,2-butadiene, 1,3-butadiene, 2-ethyll ,3-butadiene; styrene monomersincluding, for example, styrene, 2- methyl styrene, 3-methyl styrene,4-methyl styrene, 4- ethyl styrene, 4-butyl styrene; and otherpolymerizable monomers; and (2) a relatively small amount, on the orderof from about 1 percent by weight to about 8 percent by weight, of anunsaturated acid containing a terminal hydroxy group such as thea,fi-unsaturated carboxylic acids including acrylic acid, methacrylicacid, fumaric acid, maleic acid, itaconic acid, crotonic acid,isocrotonic acid, angelic acid, tiglic acid, etc. Anhydrides of suchacids, where they exist, are also of use. Other a,B-unsaturated acidsare of use and include 2- sulfoethyl methacrylate, styrene sulfonicacid, vinyl phosphonic acid, etc.

It is to be appreciated that more than one monomer may be included inthe polymerization with the a,B-unsaturated acid. An outstanding exampleof the use of more than one monomer is the polymerization of butadieneand styrene with an a,B-unsaturated acid such as acrylic acid,methacrylic acid, fumaric acid, maleic acid, or itaconic acid.Anhydrides, for example, maleic anhydride, are also of use.

THE WATER-SOLUBLE, POLYMERIC CARBOXYLIC THICKENER Also of applicationwithin the principles of the present inventive concept, either in lieuof the previously mentioned synthetic resins or in addition thereto, arewater-soluble, polymeric carboxylic thickeners which are included in theresin composition in amounts of from about 0.05 percent by weight toabout 10 percent by weight.

hydroxyamino The water soluble polymeric carboxylic thickener may beselected from a relatively large group of such materials which include,for example: polyacrylic acid; polymeric crotonic acid; copolymers ofvinyl acetate and crotonic acid; copolymers of vinyl acetate and acrylicacid; polyacrylic acid-polyacrylamide copolymers; polymethacrylic acid;polymethacrylic acidpolyacrylamide copolymers; carboxymethyl cellulose;carboxyethyl cellulose; carboxypropyl cellulose; polycarboxy-methylhydroxyethyl cellulose; alginic acid; polymers of acrylic acid andacrylic acid esters; polymers of B-unsaturated carboxylic acids such asitaconic acid; etc. These water soluble, polymeric, carboxylicthickeners may be used in their acid forms but normally it is preferredto use their water-soluble, neutralized salts, that is, their sodium,potassium, lithium, ammonium, or like water soluble salts.

THE SURFACTANTS On occasion, anionic and nonionic surfactants are addedto the synthetic resin composition to create, enhance or to augment thetriggering action which initiates the coagulation and precipitation ofthe synthetic resin. Such anionic and nonionic surfactants are includedin the synthetic resin composition in amounts ranging from about 0.01percent to about 5 percent by weight, based on the weight of thesynthetic resin solids.

Typical examples of such surfactants are: the alkyl aromatic sulfonicacids, alkyl sulfonic acids, the carboxylic acids, and other surfactantssuch as, for example, dodecyl benzene sulfonate, octyl benzenesulfonate, hexyl benzene sulfonate, octadecyl benzene sulfonate, octylsulfonate, hexyl sulfonate, dodecyl sulfonate, octadecyl sulfonate, andthe sodium and potassium fatty acid soaps containing from 5 to 18 carbonatoms. Other anionic surfactants include sodium p-lmethyl alkyl benzenesulfonates in which the alkyl group contains from 10 to 16 carbon atoms,the sodium di-n-alkyl sulfosuccinates in which the alkyl groups containfrom 4 to 12 carbon atoms, the potassium nalkyl malonates in which thealkyl group contains from 8 to 18 carbon atoms, the potassium alkyltricarboxylates in which the alkyl group contains from 6 to 14 carbonatoms, the alkyl betaines in which the alkyl group contains from 6 to 14carbon atoms, the ether alcohol sulfates, sodium n-alkyl sulfates,containing from 6 to 18 carbon atoms, etc.

Non-ionic surfactants which are-useful within the principles of thepresent invention possess non-ionizing hydrophilic groups and includesuch surface-active agents as fatty acid mono-esters of polyglycerol andpentaerythritol. Specific examples are glycerol monostearate, glycerolmono-laurate, pentaerytritol monostearate, pentaerytritrol,mono-laurate, etc. Others include glycol esters of fatty acids, preparedby treating the acid with ethylene oxide. Specific useful surfactantsinclude: nonyl phenoxy poly (ethyleneoxy) ethanol; nonyl phenolpolyglycol ether alcohol; polyethylene glycol monolaurate;polyoxyethylene oleyl ether; ethylene oxide condensates of castor oil;polyglycol palmitate amide; ethoxylated alkyl phenol; lauricdiethanolamide; octyl phenoxy polyethoxy ethanol; difunctionalblock-polymers terminating in primary hydroxy groups; etc.

The specific surfactant which is selected for use in the-resincomposition does not relate to the essence of THE POLYVALENT METALCOMPLEX COORDINATION COMPOUND The polyvalent metal complex coordinationcompound is included in the resin composition in an amount equal to fromabout 0.01 percent by weight to about percent by weight, based on theweight of the previously mentioned synthetic resin or polymer solids.

Examples of polyvalent metal complex coordination compounds ofparticular applicability when the porous or absorbent materials arepretreated with acidic media are: ammonium carbonato zirconate (NH4)3 l3)3]' 2 ammonium heptafluoro zirconate (NH4)3 l 7] potassium tetracyanozincate K [Zn(CN) sodium tetrahydroxo zincate sodium tetrahydroxoaluminate potassium trioxalato aluminate As defined herein, a metalcomplex coordination compound is one of a number of types of metal com-45 plex compounds, usually made by addition of organic or inorganicatoms or groups to simple inorganic compounds containing the metal atom.Coordination compounds are therefore essentially compounds to whichatoms or groups are added beyond the number possible of explanation onthe basis of electrovalent linkages, or the usual covalent linkages,wherein each of the two atoms linked donate one electron to form theduplet. In the cases of the coordination compounds, the coordinate atomsor groups are linked to the atoms of the coordination compound, usuallyby coordinate valences, in which both the electrons in the bond arefurnished by the linked atoms of the coordinated group.

Other examples of polyvalent metal complex coordi- 6O pentammine chlorochromium chloride crowns Cl] c1 hexammine nickel chloride tetramminedinitro cobalt nitrate l s)4( 2)2] a)3 hexammine cobalt chloridehexammine cobalt iodide hexammine cobalt nitrate 3)s] ah hexamminecobalt sulfate hexammine cobalt bromide hexammine nickel bromidehexammine nickel chlorate hexammine nickel iodide hexammine nickelnitrate tetrammine zinc carbonate tetrammine zinc sulfate tetramminezinc nitrate diammine zinc chloride tetrammine zinc chloride diamminecopper acetate tetrammine copper sulfate tetrammine copper hydroxideammonium tetra thiocyanato diammine chromate hexammine chromium chloride[Cr(NH C1 H O chloro pentammine chromium chloride As defined herein, ametal ammine complex coordination compoumd is one of a number of typesof metal complex compounds, usually made by addition of organic orinorganic atoms or groups such as ammonia (Ni-l to simple inorganiccompounds containing the metal atom. Coordination compounds aretherefore essentially compounds to which atoms or groups are addedbeyond the number possible of explanation on the basis of electrovalentlinkages, or the usual covalent linkages, wherein each of the two atomslinked donate one electron to form the duplet. In the case of thecoordination compounds, the coordinated atoms or groups are linked tothe atoms of the coordination compound, usually by coordinate valences,in which both the electrons in the bond are furnished by the linkedatoms of the coordinated group.

THE WATER-SOLUBLE, lONICALLY-ACTIVE SALT The water-soluble, ionicallyactive ammonium or alkali metal salt of an acid (to be defined moreparticularly hereinafter) is present in the resin composition in anamount of from about 5 percent to about 90 percent molecular equivalent(stoichiometric basis) of the polyvalent metal which is present andwhich is to be precipitated ,or sequestered. That is to say, forexample, if there is one mole of the polyvalent metal present, thenthere is from about 0.05 to 0.90 mole of the watersoluble, ionicallyactive ammonium or alkali metal salt present.

Ammonium and alkali metal salts of acids naturally are selected from thegroup consisting of ammonium, lithium, sodium and potassium salts. Ofthese, ammonium is preferred. As a matter of fact, in many cases wherethere is sufficient ammonium or alkali metal hydroxide in the resincomposition, the agent may be added in the acid form rather than in thesalt form and the water-soluble, ionically active ammonium salt will beformed, in situ. The above salts generally consist of the N11,, Na,etc., and salts of acids listed below.

THE ACIDS Examples of acids suitable for application within theprinciples of the present invention are: inorganic mineral acids such asortho-phosphoric acid, hypophosphoric acid, metaphosphoric acid,triphosphoric acid, tetraphosphoric acid, chromic acid, orthoboric acid,metaboric acid, tetraboric acid, etc.; monobasic aliphatic organicacids, preferably having at least carbon atoms, such as capric acid,lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,linoleic acid, linolenic acid, etc.; dicarboxylic aliphatic organicacids such as oxalic acid, malonic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, etc.; aliphatic hydroxy acidssuch as citric acid, glycollic acid, lactic acid, malic acid, tartaricacid, etc.; monocarboxylic aromatic organic acids such as benzoic acid,o-toluic acid, m-toluic acid, p-toluic acid, phenylacetic acid, cinnamicacid, etc.; hydroxy aromatic organic acids such as salicylic acid,m-hydroxy benzoic acid, p-hydroxy benzoic acid, mandelic acid, etc.;dicarboxylic and polycarboxylic aromatic organic acids such as phthalicacid, isophthalic acid, terephthalic acid, gluconic acid, etc.

Many of these acids are frequently also classified as chelating agentsand possess the ability to form chelated compounds wherein thepolyvalent metal cations which are associated with them are renderedionically inactive and remain in solution in sequestered form.

Other acids which are more truly considered as chelating agents are alsosuitable for application within the principles of the present invention.Such chelating agents include: ethylene diamine tetraacetic acid (EDTA);ethylene diamine tetrapropionic acid (EDTPA); hydroxyethyl ethylenediamine triacetic acid (HEDTA); ammonia triacetic acid (NTA); N-hydroxyethyl diethylene triamine tetraacetic acid (HDTTA); etc.

The invention will be further described by reference to the followingExamples wherein there are disclosed preferred embodiments of thepresent invention. However, it is to be appreciated that such Examplesare illustrative but not limitative of the broader aspects of theinventive concept.

EXAMPLE I A resin binder formulation suitable for bonding nonwovenfabrics having the following composition is prepared:

GAF 500-19A carboxylated butadiene-styrene resin (50% solids) GAFCorporation 12.5 Water 6.0 Anti-foam agent 0.12 External curing agentfor resin 0.55 Acrylic acid copolymer thickener Rohm and Haas Acrysol 51(10%) (ammonium salt) 1.30 Zinc tetrammine chloride (169 ml.) 10% Zn0.42

Content Plasticizer 0.60 Anionic surfactant (25%) 0.25

The values in pounds in the above Example and in all other Examplesherein represent the weight in pounds of the constituent or the solutionadded. To obtain the real weight of the added constituent, if in asolution, you must multiply by the percent solids or concentration ofthe constituent in the solution.

The viscosity of the above described composition is 1000 centipoises, asinitially prepared. The pH is on the alkaline side (9.0). A one-poundsample is exposed to air for seven days and the viscosity undesirablyincreases to 20,000 centipoises. Another one-pound sample is protectedby the addition of 001 pound of a 25 percent solution of diammoniumphosphate. The onepound sample of the protected composition is exposedto air for seven days and the viscosity increases to only 1,040centipoises. There is no excessive thickening or setting-up of the resinlatex. The beneficial results of the diammonium phosphate as anantithickneing and anti-coagulating agent are notable.

EXAMPLE II A resin binder formulation suitable for bonding nonwovenfabrics having the following composition is prepared:

lauds GAF-243 carboxylated butadiene-styrene resin (50% solids) GAFCorporation 2.8 Water 0.9 Anti-foam agent 0.03 External curing agent forresin (80%) 0.1 l

Con in e Pounds Acrykic acid copolymer thickener Rohm and Haas Acrysol(l0%) (ammonium salt) 0.l8 Zinc tetrammine chloride (33 ml.) 10% Zncontent 0.083 Plasticizer 0.15 Anionic surfactant (25%) 0.03 Corrosioninhibitor 0.03

The viscosity of the above-described composition is 560 centipoises, asinitially prepared. The pH is alkaline (9.2). A 0.7-pound sample isexposed to air for 24 hours and the viscosity undesirably increases to3,200 centipoises. Another 0.7-pound sample is protected by the additionof 1 ml. of a 25 percent solution of diammonium phosphate. The 0.7-poundsample of the protected composition is exposed to air for 24 hours andthe viscosity increases to only 1,060 centipoises. There is no excessivethickening or setting-up of the resin latex. The beneficial results ofthe diammonium phosphate as an anti-thickening and anti-coagulatingagent are notable.

EXAMPLE III EXAMPLE IV The procedures of Example II are followedsubstantially as set forth therein with the exception that the 0.7-poundsample is protected by the addition of 1 ml. of a 25 percent solution ofthe ammonium salt of ethylene diamine tetraacetic acid. The sample ofthe protected" composition is exposed to air for 24 hours and theviscosity increases moderately to only 1,400 centipoises. There is noexcessive thickening or setting-up of the protected resin latex. Thebeneficial results of the ethylene diamine tetraacetic acid as anantithickening and anti-coagulating agent are notable.

EXAMPLE V The procedures of Example IV are followed substantially as setforth therein with the exception that ethylene diamine tetraacetic acidis added rather than its ammonium salt. The dispersion is sufficientlyammoniacal, that the ammonium salt is formed in situ. and subsequentlyprotects the dispersion from coagulation and precipitation. Nothickening or setting-up of the protected resin latex is noted. Theresults are generally comparable.

EXAMPLE v1 The procedures of Example II are followed substantially asset forth therein with the exception that the 0.7-pound sample isprotected by the addition of 1 ml. of a 12% percent solution of ammoniumoxalate. The sample of the protected composition is exposed to air for24 hours and the viscosity increases to only 1,600 centipoises. Thisincrease in viscosity is significantly below the unprotected sample andis still acceptable. The beneficial results of such a small amount ofammonium oxalate as an anti-thickening and anticoagulating agent arenotable.

EXAMPLE VII A resin binder formulation suitable for bonding nonwovenfabrics having the following composition is prepared:

Pounds GAP-243 carboxylated hutadiene-styrene resin (50% solids) GAFCorporation 25 Water 0.8 Anti-foam agent 0.03 External curing agent forresin (H0 Acrylic acid copolymer thickener Rohm and Haas Acrysol 51(10%) (ammonium salt) 0.l5 Zinc tetrammine chloride (30 ml.) l0% Zn0.074

content Plasticizer 0.13 Anionic surfactant (25%) 0.03 Corrosioninhibitor (20%) 0.03

The viscosity of the above-described composition is 7,400 centipoises,as initially prepared. The pH is alkaline (9.3). A 0.7-pound sample isexposed to air for 24 hours and the viscosity undesirably increases to20,000 centipoises. Another 0.7-pound sample is protected by theaddition of 4 ml. of a 25 percent solution of diammonium phosphate. Thesample of the protected" composition is exposed to air for 24 hours, andthe viscosity decreases. There is no evidence of any thickening orsetting-up of the resin latex. The beneficial results of the diammoniumphosphate as an antithickening and anti-coagulating agent are notable.

EXAMPLE VIII A resin binder formulation suitable for bonding nonwovenfabrics having the following composition is prepared:

Pounds GAF243 carboxylated butadiene-styrene resin (50% solids) GAFCorporation 2.5 De-ionized water 0.8 Anti-foam agent 0.03 Externalcuring agent for resin (80%) 0.l0 Acrylic acid copolymer thickener Rohmand Haas Acrysol 5l (10%) (ammonium 0.15

salt) Zinc tetrammine chloride l6) ml.) l0% Zn 0.074

content Plasticizer 0.13 Anionic surfactant (25%) 0.03

The viscosity of the above-described composition is 7,400 centipoises,as initially prepared. The pH is alkaline (9.4). A 0.7-pound sample isexposed to air for 24 hours and the viscosity increases to 20,000centipoises. Another 0.7-pound sample is protected by the addition of 1ml. of a 25 percent solution of diammonium phosphate. The 0.7-poundsample of the protected composition is exposed to air for 25 hours andthe viscosity decreases to 2,800 centipoises. The beneficial results ofthe diammonium phosphate as an anti-thickening and anti-coagulatingagent are notable.

EXAMPLE IX A fibrous card web weighing about 750 grains per square yardand comprising percent bleached rayon fibers 1.5 denier and 1 9/16inches in length is intermittently print bonded by the rotogravureprocess using an engraved roll having a diamond print pattern therein.Apparatus such as illustrated in the FIGURE is used. There areapproximately four lines per inch in each of two directions, crossing toform a diamond pattern and each set of lines is approximately 30 to thecross axis of the fibrous web. The width of each line, as measured onthe engraved print roll, is 0.024 inch. The composition by weight of theresin binder formulation used for the intermittent print bonding is:

1. 15 pounds of a 50 percent solids latex of GAF-243 terpolymer of 46percent butadiene, 51 percent styrene and approximately 2 percentalpha-beta unsaturated carboxylic acid;

2. 5 pounds of de-ionized water;

3. 0.15 pound of an anti-foam agent;

4. 0.60 pound of 80 percent solution of an external curing agent for theresin;

5. 0.75 pound of a plasticizer for the resin;

6. 0.85 pound of a percent solution of a polymeric thickening agent Rohm& Haas Acrysol 51, a copolymer of acrylic acid (ammonium salt) 7. 0.15pounds of an anionic surfactant percent) 8. 0.2 pound of blue coloring9. 0.15 pound of an anti-corrosion agent 10. 190 ml. (0.47 pound) ofzine tetrammine chloride To a 5.6-pound sample of the above compositionis added 0.03 pounds of a 25 percent solution of diammonium phosphate.The viscosity of the resulting composition, as initially prepared, is400 centipoises. The pH is 9.

The fibrous card web is pretreated or premoistened with a large amountof water to an extent of 250 percent moisture, based on the weight ofthe fibers in the web. The extra dilution with water is sufficient todestroy the stability of the resin dispersion when it is applied to thefibrous web by a rotogravure printing process and the resin dispersionimmediately coagulates and precipitates in place on the very wet fibrousweb. The printed web is then processed, treated and cured as describedin the previous referred-to patent applications.

The width of the binder line in the finished bonded nonwoven product isnot more than about 0.048 inch which represents a controlled totalmigration of not more than about 100 percent.

The control over the bonding operation and production procedure is verygood. At no time is there any evidence of premature coagulation orprecipitation in the bath. There is substantially no thickening orsetting-up of the synthetic resin dispersion in the bath prior to beingapplied to the nonwoven fabric.

The resulting bonded nonwoven fabric has excellent strength, excellentsoftness, and excellent drape and hand.

EXAMPLE X The procedures of Example IX are followed substantially as setforth therein with the exception that an increased amount of 0.06 poundof the 25 percent solution of diammonium phosphate is added to the 5.6-pound sample of the resin binder composition. The pH of the resultingcomposition is 9.2 and the viscosity is 440 centipoises. The results aregenerally comparable to those obtained in Example IX and the resultingbonded nonwoven fabric has excellent strength, excellent softness andexcellent drape and hand.

EXAMPLE XI The procedures of Example IX are followed substantially asset forth therein with the exception that a further increased amount of0.12 pound of 25 percent solution of diammonium phosphate is added to a5.6- pound sample of the resin binder composition. The pH of theresulting dispersion is 9.2 and its viscosity is 360 centipoises.

There is substantially no excessive thickening, coagulating, orpremature coagulation of the resin latex in the bath. Calculation of theamount of diammonium phosphate, however, indicates that there is morethan its stoichiometric equivalent present and the excess diammoniumphosphate interferes seriously subsequently upon printing of the webfibrous web and control is lost over the migration and lateral spread ofthe binder.

EXAMPLE XII The procedures of Example IX are followed substantially asset forth therein with the following synthetic resin formulation:

Pounds GAP-243 carboxylated butadienestyrene resin (50%) solids) GAFCorporation 300 Anti-foam agent 4 De-ionized water 100 Resin curingagent 12 Resin plasticizer 15 Acrylic acid co-polymer thickening agentRohm and Haas Acrysol 51 (10%) (ammonium l5 salt) Zinc tetramminechloride 10% Zn 6.12 Anionic surfactant 0.50 Anti'corrosion agent 0.8Diammonium phosphate (25%) 1.5

The control of the application of the protected synthetic resincomposition to the fibrous web is very good. The viscosity of thesynthetic resin composition at the outset is 600 centipoises and thisvalue does not change materially throughout the operation of the binderapplication. There is no evidence of any premature coagulation orprecipitation of the resin binder composition in the bath and there isno undesirable thickening or setting up of the resin prior to beingapplied to the fibrous web. The resulting bonded nonwoven fabric hasexcellent strength, excellent softness, and excellent drape and hand. Itis acceptable to the industry.

EXAMPLE XIII The procedures of Example I are followed substantially asset forth therein with the exception that the following synthetic resinformulation is used.

External curing agent for resin The viscosity of the dispersion asinitially prepared is 880 centipoises and the pH is 9.5. A sample of theresin is exposed to air and the viscosity thereof increases to 20,000centipoises in 24 hours.

A 0.7-pound sample of the resin dispersion is protected by the additionthereto of 1 ml. of a 25 percent solution of diammonium phosphate. After24 hours, the viscosity of the resin dispersion is 840 centipoises.After 48 hours, the viscosity increases to 1,600 centipoises.

The beneficial results of the addition of diammonium phosphate arenotable.

To another 0.7-pound sample of the above resin is added 1 ml. of a 25percent solution of ammonium citrate. After 24 hours, the viscosity ofthe dispersion is 2,000 centipoises. The beneficial results of theaddition of ammonium citrate are notable.

EXAMPLE XIV The procedures of Example IX are followed substantially asset forth therein with the exception that zinc tetrammine chloride isreplaced by:

l. Zinc tetrammine sulfate;

2. Zinc tetrammine carbonate;

3. Zinc tetrammine nitrate.

The results are generally comparable to the results obtained in ExampleIX. The bonded nonwoven fabric is processed with no productiondifficulties. There is no thickening or setting-up of the resin latex inthe applicator bath. There is no premature coagulation or precipitationin the bath of resin latex. The resulting bonded nonwoven fabric hasexcellent strength, excellent softness, and excellent hand and drape.

EXAMPLE XV The procedures of Example I are followed substantially as setforth therein with the exception that the diammonium phosphate isreplaced by:

I. ammonium benzoate;

2. ammonium palmitate 3. the sodium salt of ethylene diamminetetraacetic acid;

4. ammonium succinate;

5. sodium phosphate.

The results are generally comparable to the results obtained in ExampleI. There is no excessive thickening or setting-up of the resin latex.The beneficial results of the anti-thickening and anti-coagulating agentare notable.

EXAMPLE XVI The procedures of Example IX are followed substantially asset forth therein with the exception that the carboxylated butadienestyrene resin is replaced by:

I. National Starch 4260, a polyacrylic resin;

2. Geon 576 polyvinyl resin;

3. National Starch 22K] 1 polyvinyl acetate resin.

The results are generally comparable to the results obtained in ExampleIX. There is no excessive thickening or setting up of the resin latex inthe bath. The beneficial results of the anti-thickening andanticoagulating resin are notable. The properties of the bonded nonwovenfabric are generally comparable to those obtained in Example IX.

EXAMPLE XVII The procedures of Example IX are followed substantially asset forth therein with the exception that the polymeric thickener(Acrysol 51) is replaced by the:

1. sodium salt of Hercules carboxymethylcellulose designated as grade7H3S;

2. sodium salt of Hercules carboxymethylcellulose designated as grade7M;

3. sodium salt of Hercules carboxymethylcellulose designated as grade7L2;

4. Kelco Kelgin F alginate (sodium salt) The results are generallycomparable to the results obtained in Example IX. There is no excessivethickening or setting-up of the resin latex in the bath. There is noevidence of any premature coagulation or precipitation. The resultingbonded nonwoven fabric has excellent strength, excellent softness, andexcellent drape and hand. It is acceptable to industry.

EXAMPLE XVIII The procedures of Example I are followed substantially asset forth therein with the exception that the following composition isused:

Pounds GAF-243 Carboxylated butadiene styrene resin (50% solids) GAFCorporation 1.0 water 0.3 Acrylic acid copolymer thickener Rohm and HaasAcrysol SI 10%) (ammonium 0.l

salt) Ammonium zirconyl carbonate (10 ml. I07: ZnO 0.02 Plasticizer 0.05Anionic surfactant (25%) 0.0l

The viscosity of the above described composition is 1200 centipoises asinitially prepared. The pH is alkaline (pH 9.3 Upon exposure to air for4 days, the viscosity undesirably increases to 1920 centipoises.

A 0.67-pound sample of the above resin composition is protected by theaddition of 1.5 ml. of a 25 percent solution of diammonium phosphate. Atthe end of four days exposure to air, the viscosity has risen onlyslightly to 1,400 centipoises.

There is no excessive thickening or setting-up of the resin latexcomposition. The beneficial results of the diammonium phosphate as ananti-thickening and anticoagulating agent are notable.

EXAMPLE XIX The procedures of Example I are followed substantially asset forth therein with the exception that the following composition isused:

. Pounds GAF-243 carboxylated butadiene-styrene resin (50% solids) GAFCorporation 1.0 Water 0.3 Acrylic acid copolymer thickener Rohm and HaasAcrysol SI (10%) (ammonium 0.05

salt) Ammonium zirconyl carbonate (l5 ml. l0% ZnO,) 0.03 Plasticizer0.05 Anionic surfactant (25%) 0.01

The viscosity of the above described composition is 240 centipoises. Thecomposition is alkaline and has a pH of 9.3. Upon exposure to air for 4days, the viscosity of the composition increases to 520 centipoises.

A 0.65-pound sample of the above resin composition is protected by theaddition of 2 ml. of 25 percent diammonium phosphate. The viscosity ofthe resulting composition is 240 centipoises which, after four days,

from the spirit and scope of the invention.

We claim:

1. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereonwhich comprises: applying to porous materials a stable synthetic resincomposition having an alkaline pH and comprising: (1) from about 0.1percent to about 60 percent by weight on a solids basis of a syntheticresin; (2) from about 0.01 percent to about percent by weight, based onthe weight of said synthetic resin of a polyvalent metal complexcoordination compound; and (3) a watersoluble, ionically-active ammoniumor alkali metal salt of an acid capable of being chemically convertedinto an ionically inactive polyvalent metal salt of said acid bychemical reaction and precipitation or sequestration of said polyvalentmetal salt, said salt being capable of sequestering or precipitating themetal in said polyvalent metal complex coordination compound and beingpresent in an amount of from about 5 percent to about 90 percentmolecular equivalent on a stoichiometric basis of said polyvalent metaland substantially immediately destroying the the stability of saidsynthetic resin composition to coagulate and precipitate the resin onsaid porous materials under controlled migration conditions.

2. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the stability of said synthetic resincomposition is destroyed by diluting the same substantially immediatelyafter it is applied to said porous materials.

3. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the stability of said synthetic resincomposition is destroyed by acidifying the same substantiallyimmediately after it is applied to said porous materials.

4. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the coordination compound is a polyvalentmetal ammine complex coordination compound.

5. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of phosphoric acid.

6. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is diammonium phosphate.

7. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of a dicarboxylic aliphatic acid.

8. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium oxalate.

9. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of an aliphatic hydroxy acid.

10. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium citrate.

11. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of a monocarboxylic aromatic acid.

12. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium benzoate.

13. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of a monobasic aliphatic organic acid havingat least 10 carbon atoms.

14. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium palmitate.

15. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereonwhich comprises: applying to porous materials a stable synthetic resincomposition having an alkaline pH and comprising: (1) from about 0.1percent to about 60 percent by weight on a solids basis of a syntheticresin; (2) from about 0.01 percent to about 5 percent by weight,based'on the weight of said synthetic resin of a polyvalent meta]complex coordination compound; (3) a water-soluble, ionically activeammonium or alkali metal salt of an acid capable of being chemicallyconverted into an ionically inactive polyvalent metal salt of said acidby chemical reaction and precipitation or sequestration 'of saidpolyvalent metal salt, said salt being capable of sequestering orprecipitating the metal in said polyvalent metal complex coordinationcompound and being present in an amount of from about 5 percent to aboutpercent molecular equivalent on a stoichiometric basis of saidpolyvalent metal and (4) a water-soluble polymeric carboxylic thickener;and substantially immediately destroying the stability of said syntheticresin composition to coagulate and precipitate the resin on said porousmaterials under controlled migration conditions.

16. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereonwhich comprises: applying to porous materials a stable synthetic resincomposition having an alkaline pH and comprising: (1) from about 0.1percent to about 60 percent by weight on a solids basis of a syntheticresin; (2) from about 0.01 percent to about 5 percent by weight, basedon the weight of said synthetic resin of a polyvalent metal complexcoordination compound; (3) a water-soluble, ionically active ammonium oralkali metal salt of an acid capable of being chemically converted intoan ionically inactive polyvalent metal salt of said acid by chemicalreaction and precipitation or sequestration of said polyvalent metalsalt, said salt being capable of sequestering or precipitating the metalin said polyvalent metal complex coordination compound and being presentin an amount of from about 5 percent to about percent molecularequivalent on a stoichiometric basis of said polyvalent metal; (4) awater-soluble polymeric carboxylic thickener; and (5) a surfactant, andsubstantially immediately destroying the stability of said syntheticresin composition to coagulate and precipitate the resin on said porousmaterials under controlled migration conditions.

1. A METHOD OF APPLYING A STABLE SYNTHETIC RESIN COMPOSITION HAVING ANALKALINE PH TO POROUS MATERIALS AND CONTROLLING THE MIGRATION THEREONWHICH COMPRISES: APPLYING TO POROUS MATERIALS A STABLE SYNTHETIC RESINCOMPOSITION HAVING AN ALKALINE PH AND COMPRISING: (1) FROM ABOUT 0.1PERCENT TO ABOUT 60 PERCENT BY WEIGHT ON A SOLIDS BASIS OF A SYNTHETICRESIN; (2) FROM ABOUT 0.01 PERCENT TO ABOUT 5 PERCENT BY WEIGHT, BASEDON THE WEIGHT OF SAID SYNTHETIC RESIN OF A POLYVALENT METAL COMPLEXCOORDINATION COMPOUND; AND (3) A WATER-SOLUBLE IONICALLY-ACTIVE AMMONIUMOR ALKALI METAL SALT OF AN ACID CAPABLE OF BEING CHEMICALLY CONVERTEDINTO AN IONICALLY INACTIVE POLYVALENT METAL SALT OF SAID ACID BYCHEMICAL REACTION AND PRECIPITATION OR SEQUESTRATION OF SAID POLYVALENTMETAL SALT, SAID SALT BEING CAPABLE OF SEQUESTERING OR PRECIPITATING THEMETAL IN SAID POLYVALENT METAL COMPLEX COORDINATION COMPOUND AND BEINGPRESENT IN AN AMOUNT OF FROM ABOUT 5 PERCENT TO ABOUT 90 PERCENTMOLECULAR EQUIVALENT ON A STOICHIOMETRIC BASIS OF SAID POLYVALENT METALAND SUBSTANTIALLY IMMEDIATELY DESTROYING THE THE STABILITY OF SAIDSYNTHETIC RESIN COMPOSITION TO COAGULATE AND PRECIPITATE THE RESIN ONSAID POROUS MATERIALS UNDER CONTROLLED MIGRATION CONDITIONS.
 2. A methodof applying a stable synthetic resin composition having an alkaline pHto porous materials and controlling the migration thereon as defined inclaim 1 wherein the stability of said synthetic resin composition isdestroyed by diluting the same substantially immeDiately after it isapplied to said porous materials.
 3. A method of applying a stablesynthetic resin composition having an alkaline pH to porous materialsand controlling the migration thereon as defined in claim 1 wherein thestability of said synthetic resin composition is destroyed by acidifyingthe same substantially immediately after it is applied to said porousmaterials.
 4. A method of applying a stable synthetic resin compositionhaving an alkaline pH to porous materials and controlling the migrationthereon as defined in claim 1 wherein the coordination compound is apolyvalent metal ammine complex coordination compound.
 5. A method ofapplying a stable synthetic resin composition having an alkaline pH toporous materials and controlling the migration thereon as defined inclaim 1 wherein the water-soluble, ionically active salt of an acid isan ammonium salt of phosphoric acid.
 6. A method of applying a stablesynthetic resin composition having an alkaline pH to porous materialsand controlling the migration thereon as defined in claim 1 wherein thewater-soluble, ionically active salt of an acid is diammonium phosphate.7. A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of a dicarboxylic aliphatic acid.
 8. Amethod of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium oxalate.
 9. A method of applying a stable syntheticresin composition having an alkaline pH to porous materials andcontrolling the migration thereon as defined in claim 1 wherein thewater-soluble, ionically active salt of an acid is an ammonium salt ofan aliphatic hydroxy acid.
 10. A method of applying a stable syntheticresin composition having an alkaline pH to porous materials andcontrolling the migration thereon as defined in claim 1 wherein thewater-soluble, ionically active salt of an acid is ammonium citrate. 11.A method of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is an ammonium salt of a monocarboxylic aromatic acid.
 12. Amethod of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium benzoate.
 13. A method of applying a stablesynthetic resin composition having an alkaline pH to porous materialsand controlling the migration thereon as defined in claim 1 wherein thewater-soluble, ionically active salt of an acid is an ammonium salt of amonobasic aliphatic organic acid having at least 10 carbon atoms.
 14. Amethod of applying a stable synthetic resin composition having analkaline pH to porous materials and controlling the migration thereon asdefined in claim 1 wherein the water-soluble, ionically active salt ofan acid is ammonium palmitate.
 15. A method of applying a stablesynthetic resin composition having an alkaline pH to porous materialsand controlling the migration thereon which comprises: applying toporous materials a stable synthetic resin composition having an alkalinepH and comprising: (1) from about 0.1 percent to about 60 percent byweight on a solids basis of a synthetic resin; (2) from about 0.01percent to about 5 percent by weight, based on the weight of saidsynthetic resin of a polyvalent metal complex coordination compound; (3)a water-soluble, ionically active ammonium or alkali metal salt of anacid capable of being chemically converted into an ionically inactivepolyvalent metal salt of said acid by chemical reaction andprecipitation or sequestration of said polyvalent metal salt, said saltbeing capable of sequestering or precipitating the metal in saidpolyvalent metal complex coordination compound and being present in anamount of from about 5 percent to about 90 percent molecular equivalenton a stoichiometric basis of said polyvalent metal and (4) awater-soluble polymeric carboxylic thickener; and substantiallyimmediately destroying the stability of said synthetic resin compositionto coagulate and precipitate the resin on said porous materials undercontrolled migration conditions.
 16. A method of applying a stablesynthetic resin composition having an alkaline pH to porous materialsand controlling the migration thereon which comprises: applying toporous materials a stable synthetic resin composition having an alkalinepH and comprising: (1) from about 0.1 percent to about 60 percent byweight on a solids basis of a synthetic resin; (2) from about 0.01percent to about 5 percent by weight, based on the weight of saidsynthetic resin of a polyvalent metal complex coordination compound; (3)a water-soluble, ionically active ammonium or alkali metal salt of anacid capable of being chemically converted into an ionically inactivepolyvalent metal salt of said acid by chemical reaction andprecipitation or sequestration of said polyvalent metal salt, said saltbeing capable of sequestering or precipitating the metal in saidpolyvalent metal complex coordination compound and being present in anamount of from about 5 percent to about 90 percent molecular equivalenton a stoichiometric basis of said polyvalent metal; (4) a water-solublepolymeric carboxylic thickener; and (5) a surfactant, and substantiallyimmediately destroying the stability of said synthetic resin compositionto coagulate and precipitate the resin on said porous materials undercontrolled migration conditions.